Pore conductivity control at the hundred-nanometer scale: an experimental and theoretical study

We report on the observation of an unexpected mechanism that controls conductivity at the 100-nm scale on track-etched polycarbonate membranes. Transport measurements of positively charged methyl viologen performed by absorption spectroscopy under various pH conditions demonstrate that for 100-nm-diameter pores at pH 2 conductivity is blocked, while at pH 5 the ions move through the membrane according to diffusion laws. An oppositely charged molecular ion, naphthalene disulfonate, in the same membrane, shows the opposite trend: diffusion of the negative ion at pH 2 and very low conductivity at pH 5. The influence of parameters such as ionic strength and membrane surface coating are also investigated. A theoretical study of the system shows that at the 100-nm scale the magnitude of the electric field in the vicinity of the pores is too small to account for the experimental observations; rather, it is the surface trapping of the mobile ion (Cl- or Na+) that gives rise to the observed control of the conductivity. This surprising effect has potential applications for high-throughput separation of large molecules and bio-organisms.     

Evanescent wave cavity ringdown spectroscopy: a platform for the study of supported lipid bilayers

Evanescent wave cavity ringdown spectroscopy (EW-CRDS) is advocated as an approach for monitoring the formation of supported lipid bilayers (SLBs) on quartz substrates in situ and for the quantitative study of fast molecular adsorption kinetics at the resulting modified biomimetic surface. This approach is illustrated using SLBs of 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP). Complementary atomic force microscopy (AFM) and quartz crystal microbalance with dissipation (QCM-D) measurements confirm the formation of bilayers on quartz. The subsequent interaction of the porphyrin, 5,10,15,20-tetraphenyl-21H,23H-porphine-p,p',p',p'-tetrasulfonic acid tetrasodium hydrate (TPPS) with the cationic bilayer-modified silica surface has been studied using EW-CRDS combined with an impinging-jet to deliver analyte to the surface in a well-defined manner. The adsorption of TPPS to the bilayer was kinetically controlled and the adsorption rate constant was found to be 1.7 (±0.6) × 10(-4) cm s(-1) from finite element modeling of the jet hydrodynamics and associated convective-diffusion equation, coupled to a first-order surface process describing adsorption. These proof-of-concept studies provide a platform for the investigation of molecular processes at biomembranes using EW-CRDS for chemical species showing optical absorbance in the visible and ultraviolet range.     

Added dietary sulfur and molybdenum has a greater influence on hepatic copper concentration,intake, and performance in Holstein-Friesian dairy cows offered a grass silage- rather than corn silage-based diet

To test the hypothesis that the metabolism of Cu in dairy cows is affected by basal forage and added S and Mo, 56 dairy cows that were 35 (standard error ± 2.2) days postcalving and yielding 38.9 kg of milk/d (standard error ± 0.91) were offered 1 of 4 diets in a 2 × 2 factorial design for a 14-wk period. The 4 diets contained approximately 20 mg of Cu/kg of dry matter (DM), and had a corn silage-to-grass silage ratio of 0.75:0.25 (C) or 0.25:0.75 (G) and were either unsupplemented (?) or supplemented (+) with an additional 2 g of S/kg of DM and 6.5 mg of Mo/kg of DM. We found an interaction between forage source and added S and Mo on DM intake, with cows offered G+ having a 2.1 kg of DM lower intake than those offered G?, but no effect on the corn silage-based diets. Mean milk yield was 38.9 kg/d and we observed an interaction between basal forage and added S and Mo, with yield being decreased in cows offered G+ but increased on C+. No effect of dietary treatment on milk composition or live weight was noted, but body condition was lower in cows fed added S and Mo irrespective of forage source. We found an interaction between forage source and added S and Mo on milk somatic cell count, which was higher in cows offered G+ compared with G?, but not in cows fed the corn silage-based diets, although all values were low (mean values of 1.72, 1.50, 1.39, and 1.67 log₁₀/mL for C?, C+, G?, and G+, respectively). Mean plasma Cu, Fe, and Mn concentrations were 13.8, 41.3, and 0.25 µmol/L, respectively, and were not affected by dietary treatment, whereas plasma Mo was 0.2 µmol/L higher in cows receiving added S and Mo. The addition of dietary S and Mo decreased liver Cu balance over the study period in cows fed either basal forage, but the decrease was considerably greater in cows receiving the grass silage-based diet. Similarly, hepatic Fe decreased more in cows receiving G than C when S and Mo were included in the diet. We concluded that added S and Mo reduces hepatic Cu reserves irrespective of basal forage source, but this decrease is considerably more pronounced in cows receiving grass silage- than corn silage-based rations and is associated with a decrease in intake and milk performance and an increase in milk somatic cell count.     

Low energy electron excited nanoscale luminescence spectroscopy of erbium doped AIN

We have investigated the optical activity of Er³⁺ ions in AlN via depth-resolved, (5 nm to 250 nm), low energy electron-excited nanoscale (LEEN) luminescence spectroscopy and compared it with the luminescence of an Er-free AlN film. For the Er-free film, there was no emission in the IR from the AlN at any depth, and at higher energies we measured only a broad, weak feature between 1.7–3.25 eV along with an O defect related feature at 3.8 eV, which is significantly enhanced toward the surface. We found strong emission in the AlN:Er films from the first excited → ground state transition of Er³⁺ at 0.80 eV along with many other excited state transitions, although the features are broad compared to those of GaN:Er. The AlN:Er luminescence saturates near a concentration of 10²¹ cm⁻³, at which point we also observe enhanced O defect related luminescence uniformly distributed throughout the film. This finding suggests a role for O in activating the Er at low Er concentrations, while inhibiting the Er activity at high O concentrations.     

Fish, fishing, and pollutant reduction in the Baltic Sea

The Baltic Sea is heavily polluted yet supports major commercial fisheries for cod (Gadus morhua), herring (Clupea harengus), and sprat (Sprattus sprattus). Emissions of persistent organic pollutants, such as polychlorinated biphenyls (PCBs) and DDT, were high during the 1960s and 1970s, and concentrations in fish and other fauna are still significant. Several models of the fluxes of these pollutants among the water, sediment, and atmosphere have been developed, but these generally omit the roles of fish and fisheries. We show that the standing stock of the most abundant fish species in the Baltic Sea was a sink for 260 kg of PCBs in the late 1980s to early 1990s and that the fishery removed as much or more PCB (31 kg yr(-1))than other budget components (e.g., degradation in the water column). Accounting for fish and fisheries could increase our understanding of the fluxes of pollutants, and banning the discard of highly contaminated organs such as cod liver could be part of the pollution management.     

Enhanced Bioavailability of Eicosapentaenoic Acid from Fish Oil After Encapsulation Within Plant Spore Exines as Microcapsules

Benefits of eicosapentaenoic acid (EPA) can be enhanced by raising their bioavailability through microencapsulation. Pollen can be emptied to form hollow shells, known as exines, and then used to encapsulate material, such as oils in a dry powder form. Six healthy volunteers ingested 4.6 g of fish oil containing 20% EPA in the form of ethyl ester first alone and then as 1:1 microencapsulated powder of exines and fish oil. Serum bioavailability of EPA was measured by area under curve (AUC_0–24). The mean AUC_0–24 of EPA from ethyl ester with exine (M = 19.7, SD = 4.3) was significantly higher than ethyl ester without exines (M = 2, SD = 1.4, p < 0.01).The bioavailability of EPA is enhanced by encapsulation by pollen exines.     

Sorption of pyrene to dissolved humic substances and related model polymers. 2. Solid-phase microextraction (SPME) and fluorescence quenching technique (FHT) as analytical methods

Sorption coefficients for pyrene on dissolved humic substances and on poly(acrylic acid) esters as well-defined model polymers were determined using solid-phase microextraction (SPME) and the fluorescence quenching technique (FQT). The results of both analytical methods were compared and theoretically evaluated, which led to the conclusion that the sorption coefficients measured by SPME and FQT are inevitably different: SPME measures activity-based and FQT concentration-based sorption coefficients. The environmental relevance of the two types of sorption coefficients is discussed. FQT is inappropriate to measure sorption coefficients for pyrene with the synthetic sorbents. Inspection of the vibrational structure of the fluorescence spectra of those solutions indicates a highly hydrophobic microenvironment of pyrene. This can be explained by an intra- or intermolecular agglomeration of hydrophobic moieties forming a favorable host for hydrophobic solutes.     

Fe-Zeolite as on-Site Regenerable Adsorber for Chlorohydrocarbons in Groundwater – from Laboratory to Pilot Test

This study describes the design and upscaling of an on-site regenerable adsorbent fixed bed of Fe-loaded MFI zeolite for removal of chlorinated hydrocarbons (CHCs) from contaminated groundwater from laboratory studies to pilot scale. The zeolite has an excellent adsorption performance for the hydrophilic CHCs and can be regenerated on-site by flushing with H₂O₂ to degrade adsorbed contaminants by a catalytic Fenton-like reaction. In the pilot test, the Fe-zeolite (30 kg) maintained its performance over treatment of 1470 m³ of groundwater in 12 adsorption/regeneration cycles.     

A Multi-Criteria Decision Analysis Technique for Stochastic Task Criticality in Project Management

Inherent in project management is the risk that a project fails to meet planned completion deadlines due to delays experienced in individual tasks. As such, certain critical tasks may be candidates for risk management (e.g., the allocation of additional resources such as labor, materials, and equipment) to prevent delays. A common means to identify such critical tasks is with the critical path method (CPM), which identifies a path of tasks in a project network that, when delayed, result in project delays. This work offers a complementary, stochastic approach to CPM that ranks tasks according to their effect on the project completion time distribution, when the distributions of task completion time are delayed. The new hybrid approach is based on the use of a Monte Carlo simulation and a multi-criteria decision analysis technique. Monte Carlo simulation allows for approximating the cumulative distribution function of the total duration of the project, while the multi-criteria decision analysis technique is used to compare and rank the tasks across percentiles of the resulting project completion time distributions. Doing so allows for different percentile weighting schemes to represent decision maker risk preferences. The suggested approach is applied to two project network examples. The examples illustrate that the proposed approach highlights some tasks as risky, which may not always lie on the critical path as identified by CPM. This is valuable for practicing managers as it allows them to properly consider their risk preferences when determining task criticality based on the distribution of project completion time (e.g., emphasizing median vs. upper tail completion time).     

The influence of electron momentum on the shape of backscatter peaks in gamma-ray spectrometers

The shape and intensity of backscatter peaks in pulse-height spectra have a complicated dependence on details of detector design, gamma-ray energy and geometry. In addition they show a remarkably strong systematic dependence on the atomic number of the scattering material and even manifest specifically solid state effects. The external backscatter peak can be regarded as a weighted composite of Compton profiles with an unexploited potential for revealing small changes in the electron momentum spectra of the scattering material. Its sensitivity in this role could be improved by the use of detectors with very thick depletion layers and by a redesign of the coldfinger to diminish the internal backscatter peak. By reduction of the source energy and the use of a small absorber post, the system evolves into a new type of Compton-profile spectrometer of outstanding efficiency and small dimensions.